1. New methods for remote sensing of altitude profiles of the O( 3 P), O 3 and CO 2 in the daytime mesosphere and lower thermosphere Valentine A. Yankovsky Saint - Petersburg State University St. Petersburg, Russia 2 nd International Conference and Exhibition on Satellite & Space Missions July 21-23, 2016 Berlin, Germany

2. 2  In this study, we propose new methods using of proxies for retrieving the [O( 3 P)], [O 3 ] and [CO 2 ] vertical distributions in the daytime mesosphere and lower thermosphere.

3. 3  One of the main requirements for the proxy is that the measured value should be directly related to a variable of our interest while, at the same time, the influence of themselves on [O( 3 P)], [O 3 ] and [CO 2 ] should be minimal. Satellite, Berlin, 2016  In this study, we propose new methods using of proxies for retrieving the [O( 3 P)], [O 3 ] and [CO 2 ] vertical distributions in the daytime mesosphere and lower thermosphere.

4. 4 Around us there are a lot of proxies, if you look closely! Satellite, Berlin, 2016  One of the main requirements for the proxy is that the measured value should be directly related to a variable of our interest while, at the same time, the influence of themselves on [O( 3 P)], [O 3 ] and [CO 2 ] should be minimal.  In this study, we propose new methods using of proxies for retrieving the [O( 3 P)], [O 3 ] and [CO 2 ] vertical distributions in the daytime mesosphere and lower thermosphere.

5.  Problem with the measurement of the O( 3 P), O 3 and CO 2 densities in day time has not been solved so far. Meanwhile the emission bands originating from the electronical-vibrationally excited molecules, O 2 (b 1 Σ⁺ g, v=0, 1 and 2), depend on these small components. It allows to use the emissions bands as proxies of the O(3P), O3 and CO2 in the MLT region. 5 Around us there are a lot of proxies, if you look closely! Satellite, Berlin, 2016  One of the main requirements for the proxy is that the measured value should be directly related to a variable of our interest while, at the same time, the influence of themselves on [O( 3 P)], [O 3 ] and [CO 2 ] should be minimal.  In this study, we propose new methods using of proxies for retrieving the [O( 3 P)], [O 3 ] and [CO 2 ] vertical distributions in the daytime mesosphere and lower thermosphere.

6. 6 Around us there are a lot of proxies, if you look closely!  One of the main requirements for the proxy is that the measured value should be directly related to a variable of our interest while, at the same time, the influence of themselves on [O( 3 P)], [O 3 ] and [CO 2 ] should be minimal.  Problem with the measurement of the O( 3 P), O 3 and CO 2 densities in day time has not been solved so far. Meanwhile the emission bands originating from the electronical-vibrationally excited molecules, O 2 (b 1 Σ⁺ g, v=0, 1 and 2), depend on these small components. It allows to use the emissions bands as proxies of the O( 3 P), O 3 and CO 2 in the MLT region.  In this study, we propose new methods using of proxies for retrieving the [O( 3 P)], [O 3 ] and [CO 2 ] vertical distributions in the daytime mesosphere and lower thermosphere.

7. Objects of research: emissions from electronical – vibrationally excited levels of O 2 molecule Satellite, Berlin, 2016 7 Energy levels and states of O 2 1.63 eV 0.98 eV 0.00 eV b1Σg+b1Σg+ a1Δga1Δg X3Σg-X3Σg- v = 2 1 0 1 1 0 0 2 2 IR Atm(0,0) band Atm(0,0) band The atmospheric bands of molecular oxygen are the “classic" dayglow emissions: 762 nm Atm (0,0) and 1.27 μm IR Atm (0,0) Question: How can these and other emissions are formed in the dayglow?

8. O 2 dayglow production mechanism Satellite, Berlin, 2016 8 O2O2 O( 1 D) O 2 (b, v=0) 762 nm 630 nm Energy transfer from atoms O( 1 D), which are produced in result of the O 2 photolysis in the Schumann–Runge continuum and Lyman−  H atom, is main source of O 2 (b,v=0) and Atm band (0,0). =============== It is the conventional approach.

9. O 2 dayglow production mechanism Satellite, Berlin, 2016 9 O2O2 O 2 (b, v=2) O( 1 D) O 2 (b, v=1) O 2 (b, v=0) 762 nm 630 nm However, this process, as it turned out recently, mainly populates level O 2 (b, v=1). Consequently, energy transfer from excited molecules and atom O( 1 D) in collisions with atmospheric components plays a key role in the excitation of the Atm band (0,0).

10. O 2 dayglow production mechanism Satellite, Berlin, 2016 10 O2O2 O 2 (b, v=2) O( 1 D) O 2 (b, v=1) O 2 (b, v=0) 762 nm 630 nm As bonus the dayglow emissions from electronical- vibrationally excited molecules O 2 (b 1 Σ g +, v=0, 1 and 2) can serve also as the proxies of O( 3 P), O 3 and CO 2 in the mesosphere and lower thermosphere. ================= It is the contemporary approach!

11. O 2 dayglow production mechanism Satellite, Berlin, 2016 11 O2O2 O 2 (b, v=2) O( 1 D) O3O3 O 2 (b, v=1) O 2 (b, v=0) O 2 (a, v=0) 1.27 μm 762 nm 630 nm The conventional approach for 1.27 μm IR Atmospheric band (0, 0) of O 2 molecule is too simplistic. It gives an error of up to 50 percent for retrieve of the ozone density in mesosphere, as [Smith et al., 2013] established.

12. O 2 dayglow production mechanism Satellite, Berlin, 2016 12 O2O2 O 2 (b, v=2) O 2 (a, v=5) O( 1 D) O3O3 O 2 (b, v=1) O 2 (b, v=0) O 2 (a, v=4) O 2 (a, v=3) O 2 (a, v=2) O 2 (a, v=1) O 2 (a, v=0) 1.27 μm 762 nm 630 nm It is the contemporary approach: Population of O 2 (a 1 Δ g, v=0) level depends on all nine upper-lying excited levels. It requires taking into account above 30 aeronomical reactions with participation of main atmospheric components as O 2, N 2, O( 3 P), O 3 and CO 2.

13. Satellite, Berlin, 2016 13 YM2011 ‒ model of electronic-vibrational kinetics of excited products of O 3 and O 2 photolysis in the MLT of the Earth. We have developed the comprehensive model of kinetics of the electronically-vibrationally excited oxygen molecules (YM2011) in order to find possible O 3 and O( 3 P) proxies among these excited components. Last version of YM2011 model was published in this year.

14. Satellite, Berlin, 2016 14 Scheme of Kinetics of 10 excited levels: O( 1 D), О 2 (b 1  + g, v=0 - 2), O 2 (a 1 Δ g, v=0 - 5) on base of YM2011 model YM2011 ‒ model of electronic-vibrational kinetics of excited products of O 3 and O 2 photolysis in the MLT of the Earth. As can be seen from the scheme, the YM2011 model takes into account all of these ten excited oxygen levels.

15. Satellite, Berlin, 2016 15 YM2011 ‒ model of electronic-vibrational kinetics of excited products of O 3 and O 2 photolysis in the MLT of the Earth. Database of Rate coefficients and Quantum Yields of products for reactions involving О( 1 D), O 2 (b 1  ⁺ g, v=0 − 2) and O 2 (a 1 Δ g, v=0 − 5) Scheme of Kinetics of 10 excited levels: O( 1 D), О 2 (b 1  + g, v=0 - 2), O 2 (a 1 Δ g, v=0 - 5) on base of YM2011 model We have compiled the experimental data on the rate coefficients of energy transfer processes among excited levels of O 2 molecule, as well as quantum yields of the products of these processes, with the measured errors of these factors. The database includes 60 reactions.

16. Satellite, Berlin, 2016 16 Database of Rate coefficients and Quantum Yields of products for reactions involving О( 1 D), O 2 (b 1  ⁺ g, v=0 − 2) and O 2 (a 1 Δ g, v=0 − 5) The System of Kinetic Equations for excited species: O( 1 D), О 2 (b 1  + g, v=0 - 2), O 2 (a 1 Δ g, v=0 - 5) YM2011 ‒ model of electronic-vibrational kinetics of excited products of O 3 and O 2 photolysis in the MLT of the Earth. Scheme of Kinetics of 10 excited levels: O( 1 D), О 2 (b 1  + g, v=0 - 2), O 2 (a 1 Δ g, v=0 - 5) on base of YM2011 model Also in this work we gave the system of kinetic equations for all ten excited components and found an analytical solution of the direct problem.

17. Satellite, Berlin, 2016 17 Actualization of YM2011 model: analytical approaches and first results 1. Solution of forward problem. 2. Sensitivity study 3. Uncertainty analysis 4. Solution of inverse problem. Mean VER and their standard deviations for 150 SABER events during 22 nd September 2010. O( 1 D) О 2 (b, v=0 ) О 2 (b, v=1 ) О 2 (b, v=2 ) О 2 (b, v=1 ) О 2 (b, v=0 ) О 2 (a, v=0 ) Altitude profiles of [О 2 (b 1  ⁺ g, v=0 − 2)] depend on latitude and SZA during 21 st June 2010. where φ − the concentration of target function; x i − parameters (rate constants value, quantum yield, rate of photoexcitation, concentrations of atmospheric components, gas temperature etc.). YM2011 SABER Daytime [O 3 ] retrieved from O 2 (a, v=0) emission in the TIMED-SABER experiment is higher than the other eight satellites measurements over the altitude range 60-80 km by 20-50% as Smith and all SABER team found in 2013. The reason of overstatement is a neglecting of the electron-vibrational kinetics of O 2. In the frame of YM2011 model, the retrieved ozone profile in SABER experiment practically, would not differ from other experiments. Altitude profiles of [О 3 ] for 50 SABER events during 22 nd September 2010.

18. Sensitivity coefficient, S(proxy; O 3 ), in the forward problem. Sensitivity coefficient, S(O 3 ; proxy), in the inverse problem of [O 3 ] retrieval from proxy. 18 The 5 excited components: O( 1 D), three levels О 2 (b 1  g ⁺, v = 0 - 2) and O 2 (a 1 Δ g, v = 0) were tested as proxy of [O 3 ]. Testing of different proxies: retrieval of [О 3 ] altitude profile Uncertainties of [ O 3 ] retrievals (the limits ±  ) for different proxies: a) absolute values; b) relative values Notes: a)The predetermined reference altitude profile of [O 3 ] is presented by the dotted curve, and is taken from event SABER L2,2010, day 172, latitude 43.0, SZA=70.5, F10.7=74. b)О 2 (b 1  + g, v=1) is best proxy for [O 3 ] retrieval in the 50 – 100 km (green colour) c)O 2 (a 1 Δ g, v=0) can be used for [O 3 ] retrieval only in the range 50 – 88 km (purple colour).

19. Sensitivity coefficient, S(proxy; O( 3 P)), in the forward problem. Sensitivity coefficient, S(O( 3 P)); proxy), in the inverse problem of [O( 3 P)] retrieval from proxy. 19 The 5 excited components: O( 1 D), three levels О 2 (b 1  g ⁺, v = 0 - 2) and O 2 (a 1 Δ g, v = 0) were tested as proxy of [O( 3 P)] Testing of different proxies: retrieval of [O( 3 P)] altitude profile Uncertainties of [O( 3 P)] retrievals (the limits ±  ) for different proxies: a) absolute values; b) relative values Notes: a)The predetermined reference altitude profile of [O( 3 P)] is presented by the dotted curve, and is taken from event SABER L2,2010, day 172, latitude 43.0, SZA=70.5, F10.7=74. a)In the whole altitude range (90 – 140 km) the uncertainties of the retrieved values O( 3 P) concentrations are minimal for two proxies: О 2 (b 1  ⁺ g, v=0) and О 2 (b 1  ⁺ g, v=2) (red and violet colours).

20. Multi-channels methods for the simultaneous remote sensing of [O( 3 P)], [О 3 ] and/or [CО 2 ] altitude profiles in the mesosphere and lower thermosphere in daytime were developed. A unique feature: О 2 (b 1  ⁺ g, v=0) - a single proxy, which is sensitive to variations of the carbon dioxide density in MLT range Conclusions or Final recommendations for satellite missions 20 Sensitivity coefficient, S(О 2 (b 1  ⁺ g, v=0); parameter) in the forward problem. S( О 2 (b, v=0); CO2) The first practical attempt to retrieve the altitude profile of atomic oxygen using О 2 (b 1  ⁺ g, v=1) as a proxy was made in a Sweden rocket experiment in 2015 EGU 2016 Proxy [O( 3 P)][О 3 ][CО 2 ] Spectral channels Altitude range, kmCenter of emission band, nm О 2 (b 1  ⁺ g, v = 2) 85 - 140 ‒‒ 629 or 697 О 2 (b 1  ⁺ g, v = 1) 115 - 14050 - 100 ‒ 771 or 684 О 2 (b 1  ⁺ g, v = 0) 105 - 13080 - 10050 - 100762 or 864

21. Thank you! 21

22. Satellite observations of ozone in the upper mesosphere A. K. Smith, V. L. Harvey, M. G. Mlynczak, B. Funke, M. Garcia-Comas, M. Hervig, M. Kaufmann, E. Kyrola, M. Lopez-Puertas, McDade, С. E. Randall, J. M. Russell III, P. E. Sheese, M. Shiotani, W. R. Skinner, M. Suzuki, and K. A. Walker Abstract. Ozone profiles in the upper mesosphere (70-100 km) retrieved from nine instruments are compared. Ozone from the Sounding of the Atmosphere using Broadband Emission Radiometry (SABER) instrument is used as the basis of comparison. Other measurements are from the Halogen Occupation Experiment, the High Resolution Doppler Imager, the Michelson Interferometer for Passive Atmospheric Sounding, the Global Ozone Monitoring by Occupation of Stars, the Atmospheric Chemistry Experiment—Fourier Transform Spectrometer, the Solar Occupation For Ice Experiment, the Optical Spectrograph and InfraRed Imaging System, and the Superconducting Submillimeter-Wave Limb-Emission Sounder. Comparisons of each data set with SABER using coincident profiles indicate agreement in the basic vertical profile of ozone but also some systematic differences in daytime ozone. Ozone from the SABER 9.6 pm channel is higher than the other measurements over the altitude range 60-80 km by 20-50%. Nighttime comparisons indicate better relative agreement (<10% difference). Taking all the data, not limited to coincidences, shows the global and seasonal distributions of ozone in the upper mesosphere from each instrument. The average maximum in ozone mixing ratio is around 90-92 km during daytime and 95 km at night. There is a maximum in ozone density at night (—90 km) and during some hours of the day. The latitude structure of ozone has appreciable variations with season, particularly in the Tropical upper mesosphere. The basic latitude-altitude structure of ozone depends on local time, even when the analysis is restricted to day-only observations. Citation: Smith, A. K., et al. (2013), Satellite observations of ozone in the upper mesosphere, J. Geophvs. Res. Atmos., 118, 5803-5821, doi: 10.1002/jgrd.50445. 22